JP2006206743A - Oxygen-scavenging composition comprising cyclic olefin copolymer, and packaging material obtained using the same - Google Patents
Oxygen-scavenging composition comprising cyclic olefin copolymer, and packaging material obtained using the same Download PDFInfo
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- JP2006206743A JP2006206743A JP2005020945A JP2005020945A JP2006206743A JP 2006206743 A JP2006206743 A JP 2006206743A JP 2005020945 A JP2005020945 A JP 2005020945A JP 2005020945 A JP2005020945 A JP 2005020945A JP 2006206743 A JP2006206743 A JP 2006206743A
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- Prior art keywords
- oxygen
- composition
- deoxygenation
- polymer
- film
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- 239000000203 mixture Substances 0.000 title claims abstract description 97
- 239000005022 packaging material Substances 0.000 title claims abstract description 13
- 229920000089 Cyclic olefin copolymer Polymers 0.000 title claims abstract description 12
- 239000004713 Cyclic olefin copolymer Substances 0.000 title claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 87
- 239000001301 oxygen Substances 0.000 claims abstract description 87
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 86
- 229920000642 polymer Polymers 0.000 claims abstract description 60
- -1 norbornene compound Chemical group 0.000 claims abstract description 26
- 239000005977 Ethylene Substances 0.000 claims abstract description 23
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003085 diluting agent Substances 0.000 claims abstract description 17
- 230000002000 scavenging effect Effects 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 150000003623 transition metal compounds Chemical class 0.000 claims description 2
- 229920005672 polyolefin resin Polymers 0.000 claims 1
- 238000004806 packaging method and process Methods 0.000 abstract description 18
- 229910052723 transition metal Inorganic materials 0.000 abstract description 18
- 150000003624 transition metals Chemical class 0.000 abstract description 18
- 239000003054 catalyst Substances 0.000 abstract description 15
- 230000003635 deoxygenating effect Effects 0.000 abstract description 9
- 238000006392 deoxygenation reaction Methods 0.000 description 52
- 239000010410 layer Substances 0.000 description 48
- 239000010408 film Substances 0.000 description 33
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 230000004888 barrier function Effects 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- 230000005855 radiation Effects 0.000 description 16
- 229920001577 copolymer Polymers 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- 239000003963 antioxidant agent Substances 0.000 description 11
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 11
- 238000012545 processing Methods 0.000 description 10
- 230000003078 antioxidant effect Effects 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- 235000013305 food Nutrition 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 230000000977 initiatory effect Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- SDRZFSPCVYEJTP-UHFFFAOYSA-N 1-ethenylcyclohexene Chemical compound C=CC1=CCCCC1 SDRZFSPCVYEJTP-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000011203 carbon fibre reinforced carbon Chemical group 0.000 description 4
- 239000012785 packaging film Substances 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OXLXAPYJCPFBFT-UHFFFAOYSA-L CC1=CC(C)(C=C1)[Zr](Cl)(Cl)C1(C)C=CC(C)=C1 Chemical compound CC1=CC(C)(C=C1)[Zr](Cl)(Cl)C1(C)C=CC(C)=C1 OXLXAPYJCPFBFT-UHFFFAOYSA-L 0.000 description 3
- 229940123973 Oxygen scavenger Drugs 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229920000891 common polymer Polymers 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 229920006280 packaging film Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- VUIMBZIZZFSQEE-UHFFFAOYSA-N 1-(1h-indol-3-yl)ethanone Chemical compound C1=CC=C2C(C(=O)C)=CNC2=C1 VUIMBZIZZFSQEE-UHFFFAOYSA-N 0.000 description 2
- XHLHPRDBBAGVEG-UHFFFAOYSA-N 1-tetralone Chemical compound C1=CC=C2C(=O)CCCC2=C1 XHLHPRDBBAGVEG-UHFFFAOYSA-N 0.000 description 2
- YXWWHNCQZBVZPV-UHFFFAOYSA-N 2'-methylacetophenone Chemical compound CC(=O)C1=CC=CC=C1C YXWWHNCQZBVZPV-UHFFFAOYSA-N 0.000 description 2
- XSAYZAUNJMRRIR-UHFFFAOYSA-N 2-acetylnaphthalene Chemical compound C1=CC=CC2=CC(C(=O)C)=CC=C21 XSAYZAUNJMRRIR-UHFFFAOYSA-N 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- NTPLXRHDUXRPNE-UHFFFAOYSA-N 4-methoxyacetophenone Chemical compound COC1=CC=C(C(C)=O)C=C1 NTPLXRHDUXRPNE-UHFFFAOYSA-N 0.000 description 2
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Chemical group 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- LHEFLUZWISWYSQ-CVBJKYQLSA-L cobalt(2+);(z)-octadec-9-enoate Chemical compound [Co+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O LHEFLUZWISWYSQ-CVBJKYQLSA-L 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- QNXSIUBBGPHDDE-UHFFFAOYSA-N indan-1-one Chemical compound C1=CC=C2C(=O)CCC2=C1 QNXSIUBBGPHDDE-UHFFFAOYSA-N 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 229920000554 ionomer Polymers 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
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- 230000004048 modification Effects 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000005033 polyvinylidene chloride Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229920006126 semicrystalline polymer Polymers 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
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- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
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- JNELGWHKGNBSMD-UHFFFAOYSA-N xanthone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3OC2=C1 JNELGWHKGNBSMD-UHFFFAOYSA-N 0.000 description 2
- WWMFRKPUQJRNBY-UHFFFAOYSA-N (2,3-dimethoxyphenyl)-phenylmethanone Chemical compound COC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1OC WWMFRKPUQJRNBY-UHFFFAOYSA-N 0.000 description 1
- ZSQCNVWYBBKUHS-UHFFFAOYSA-N (2,3-dimethylphenyl)-phenylmethanone Chemical compound CC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1C ZSQCNVWYBBKUHS-UHFFFAOYSA-N 0.000 description 1
- QLNZDMTUYPQUCX-UHFFFAOYSA-N (2,3-diphenoxyphenyl)-phenylmethanone Chemical compound C=1C=CC(OC=2C=CC=CC=2)=C(OC=2C=CC=CC=2)C=1C(=O)C1=CC=CC=C1 QLNZDMTUYPQUCX-UHFFFAOYSA-N 0.000 description 1
- JRZMSOAHAJSDFK-UHFFFAOYSA-N (2-dodecoxyphenyl)-phenylmethanone Chemical compound CCCCCCCCCCCCOC1=CC=CC=C1C(=O)C1=CC=CC=C1 JRZMSOAHAJSDFK-UHFFFAOYSA-N 0.000 description 1
- CSUUDNFYSFENAE-UHFFFAOYSA-N (2-methoxyphenyl)-phenylmethanone Chemical compound COC1=CC=CC=C1C(=O)C1=CC=CC=C1 CSUUDNFYSFENAE-UHFFFAOYSA-N 0.000 description 1
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- RBKHNGHPZZZJCI-UHFFFAOYSA-N (4-aminophenyl)-phenylmethanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=CC=C1 RBKHNGHPZZZJCI-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Packages (AREA)
- Wrappers (AREA)
- General Preparation And Processing Of Foods (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
本発明は、（i）少なくとも１つの（ａ）エチレンユニットと（ｂ）未置換または置換ノルボルネン化合物ユニットから構成される環状オレフィン共重合体、（ii）遷移金属触媒、（iii）任意に光開始剤、及び（iv）任意にポリマー希釈剤を含む脱酸素組成物に関するものである。 The present invention comprises (i) a cyclic olefin copolymer composed of at least one (a) ethylene unit and (b) an unsubstituted or substituted norbornene compound unit, (ii) a transition metal catalyst, (iii) optionally photoinitiated And (iv) an oxygen scavenging composition optionally comprising a polymer diluent.
酸素感受性製品の酸素への暴露を制限すると、多くの製品の品質及び貯蔵寿命が維持、向上される。例えば、包装システムにおいて酸素感受性食品の酸素への暴露を制限することにより、該食品の品質を維持し、腐敗を遅らすことができる。更に、該包装により、製品はより長く貯蔵され、よって廃棄および補充にかかるコストが低減される。
食品包装業界では、酸素暴露を制限するために幾つかの方法が開発されている。一般的方法には、被包装物品または包装材料以外の何らかの手段、例えば、脱酸素サッシェを使用して、包装環境内の酸素を消費する方法；例えば、改質大気包装（ＭＡＰ）及び真空包装等のパッケージ内に低酸素環境を作成する方法；及び例えば、酸素バリヤーフィルムの使用等の酸素が包装環境に進入するのを防止する方法が含まれる。
Limiting the exposure of oxygen sensitive products to oxygen maintains and improves the quality and shelf life of many products. For example, limiting the exposure of oxygen-sensitive foods to oxygen in a packaging system can maintain the quality of the food and delay spoilage. In addition, the packaging allows the product to be stored longer, thus reducing the cost of disposal and replenishment.
In the food packaging industry, several methods have been developed to limit oxygen exposure. Common methods include any means other than the packaged article or packaging material, such as using a deoxygenated sachet to consume oxygen in the packaging environment; such as modified atmospheric packaging (MAP) and vacuum packaging A method for creating a low oxygen environment within the package; and a method for preventing oxygen from entering the packaging environment, such as, for example, the use of an oxygen barrier film.
脱酸素組成物を収容しているサッシェは、第二鉄状態に酸化する第一鉄組成物、吸収剤上に不飽和脂肪酸塩及び／又は金属−ポリアミド複合体を含有する。このサッシェの欠点は、パッケージにサッシェを挿入するために、追加の包装ステップを必要とすること、サッシェが破れたときに被包装品が汚染される可能性があること、及び消費者が食べる危険があることが挙げられる。
脱酸素材料を包装構造体に直接配合することも行われてきた。この方法（以下、「酸素活性バリヤー」と呼ぶ）は包装中一定の脱酸素効果を発揮することができ、パッケージの壁を介して通過した酸素を捕捉、捕集し、それよってパッケージ中の酸素レベルをできるだけ最低レベルに維持する手段を提供する。酸素活性バリヤーはパッケージの一部として無機粉末及び／又は塩を配合すると包装材料の透明性及び例えば、引裂強さ等の機械的特性を劣化させる恐れがあり、薄いフィルムを所望するときには特に加工が複雑となる。また、前記化合物及びその酸化生成物は容器中の食品により吸収され、その結果食品は人の消費に関する政府標準規格を満たさなくなることがある。
A sachet containing an oxygen scavenging composition contains a ferrous composition that oxidizes to a ferric state, an unsaturated fatty acid salt and / or a metal-polyamide composite on the absorbent. The disadvantages of this sachet are that it requires an additional packaging step to insert the sachet into the package, that the packaged goods can be contaminated when the sachet breaks, and the consumer eats It is mentioned that there is.
It has also been practiced to blend oxygen scavenging materials directly into the packaging structure. This method (hereinafter referred to as “oxygen-activated barrier”) can exert a certain deoxygenation effect during packaging, capturing and collecting oxygen that has passed through the package wall, and thus oxygen in the package. Provide a means to keep the level as low as possible. Oxygen active barriers can degrade the transparency of packaging materials and mechanical properties such as tear strength, for example, when inorganic powders and / or salts are incorporated as part of the package, especially when thin films are desired. It becomes complicated. Also, the compound and its oxidation product may be absorbed by the food in the container so that the food does not meet government standards for human consumption.
従来、脱酸素化合物の脱酸素性には、酸素とある種のエチレン不飽和炭化水素中の炭素−炭素二重結合との反応が利用されていた。遷移金属触媒及びポリマー１００ｇあたり０．０１〜１０当量のエチレン二重結合を有するエチレン不飽和炭化水素ポリマーを含有する脱酸素組成物が、例えば、特許文献１、特許文献２に開示され公知である。しかしながら、前記ポリマーは非晶質であるために可撓性包装材料を作成するために通常使用されているフィルム形成性半結晶性ポリマーとブレンドすること、加工することが困難である。さらに、場合により官能的に重要な副生成物が反応の際に生成するという問題も有する。
遷移金属と共にエチレン不飽和化合物の有効な脱酸素活性の開始を促進するために光開始剤を使用することも、例えば、特許文献３に開示され公知である。しかしながら、脱酸素ポリマーとフィルム形成性ポリマーの相容性が悪いために、ブレンド中の脱酸素ポリマーの量を制限しなければならず、生じた組成物は加工することが困難である。
優れた脱酸素性を与えるために、遷移金属触媒と共にエチレンと少なくとも１つのビニル不飽和脂環式モノマー、好ましくは、ビニルシクロヘキセン、の共重合体を使用することは、例えば、特許文献４に開示され公知である。しかしながら、重合前に、ビニルシクロヘキセンモノマーは特有な臭気を有し取り扱いにくいうえ、共重合体からの残留する未反応モノマーの完全除去が困難である。
Conventionally, a reaction between oxygen and a carbon-carbon double bond in a certain type of ethylenically unsaturated hydrocarbon has been used for the deoxygenation property of a deoxygenated compound. A deoxygenation composition containing a transition metal catalyst and an ethylenically unsaturated hydrocarbon polymer having 0.01 to 10 equivalents of an ethylene double bond per 100 g of a polymer is disclosed in, for example, Patent Document 1 and Patent Document 2, and is known. . However, because the polymer is amorphous, it is difficult to blend and process with film-forming semi-crystalline polymers that are commonly used to make flexible packaging materials. Furthermore, in some cases, there is a problem in that by-products which are important in terms of functionality are formed during the reaction.
The use of a photoinitiator to promote the initiation of effective deoxygenation activity of an ethylenically unsaturated compound with a transition metal is also disclosed, for example, in US Pat. However, due to the poor compatibility of the deoxygenated polymer and the film-forming polymer, the amount of deoxygenated polymer in the blend must be limited and the resulting composition is difficult to process.
The use of a copolymer of ethylene and at least one vinyl unsaturated alicyclic monomer, preferably vinylcyclohexene, together with a transition metal catalyst to provide excellent deoxygenation is disclosed, for example, in US Pat. It is well known. However, before polymerization, the vinylcyclohexene monomer has a characteristic odor and is difficult to handle, and it is difficult to completely remove the remaining unreacted monomer from the copolymer.
近年、前記炭素−炭素二重結合の代わりに大気酸素と反応し得る構成単位として歪んだ環状アルキレン骨格を利用する方法が報告された。詳しくは、遷移金属触媒と共にエチレンと少なくとも１つの歪んだ環状アルキレンモノマー、好ましくは、シクロペンテン、の共重合体を使用することが、例えば、特許文献５に開示され公知である。エチレン／シクロペンテン共重合体は官能的に重要な副生成物を生成することなく有意な脱酸素性を示す。しかしながら、脱酸素性は十分ではなく、脱酸素性を向上させるためには、例えば臭気のあるビニルシクロヘキセン等の炭素−炭素二重結合を側鎖中に含むモノマーを同時に共重合してエチレン／シクロペンテン／ビニルシクロヘキセンの３元共重合体とすること等が必要である。
理想的には、脱酸素組成物中に使用するためのポリマー材料は良好な加工特性を示し、直接有用な包装材料に形成され得るか、または包装材料を作成するために通常使用されているポリマーと高い相容性を有していなければならず、被包装品の色、味または臭いを損ねる副生成物を生成してはならない。最適には、該組成物から形成される包装材料は十分に脱酸素した後もその物理的特性を維持し得るものである。
Recently, a method using a distorted cyclic alkylene skeleton as a structural unit capable of reacting with atmospheric oxygen instead of the carbon-carbon double bond has been reported. Specifically, the use of a copolymer of ethylene and at least one distorted cyclic alkylene monomer, preferably cyclopentene, together with a transition metal catalyst is disclosed in, for example, Patent Document 5 and is known. The ethylene / cyclopentene copolymer exhibits significant deoxygenation without producing functionally important byproducts. However, the oxygen scavenging property is not sufficient. In order to improve the oxygen scavenging property, for example, a monomer containing a carbon-carbon double bond in the side chain, such as odorous vinylcyclohexene, is copolymerized at the same time to produce ethylene / cyclopentene. / Vinylcyclohexene terpolymer is necessary.
Ideally, the polymeric material for use in the oxygen scavenging composition exhibits good processing properties and can be formed directly into a useful packaging material or commonly used to make a packaging material Must be highly compatible and must not produce by-products that impair the color, taste or odor of the packaged goods. Optimally, the packaging material formed from the composition is capable of maintaining its physical properties after sufficient deoxygenation.
本発明は、高度の加工性、及び包装材料を形成する際に使用される一般的ポリマーへの十分な相容性を示し、単独でも、または酸素感受性製品を包装するために使用されるフィルムまたは物品の一部としても有意な脱酸素能力を有する組成物を提供することを目的としてなされたものである。 The present invention exhibits a high degree of processability and sufficient compatibility with common polymers used in forming packaging materials, either alone or as a film or film used for packaging oxygen sensitive products. The purpose of the present invention is to provide a composition having significant deoxygenation ability as part of an article.
本発明は、環状アルキレン骨格を構成する炭素原子間を連結して拘束することで、より歪んだ構造にある、（i）少なくとも１つの（ａ）エチレンユニットと（ｂ）未置換または置換ノルボルネン化合物ユニットから構成される環状オレフィン共重合体が、（ii）遷移金属触媒、（iii）任意に光開始剤、及び（iv）任意にポリマー希釈剤と組み合わせることにより、高度の加工性、包装材料を形成する際に使用される一般的ポリマーへの十分な相容性をもち、単独でも、または酸素感受性製品を包装するために使用されるフィルムまたは物品の一部としても有意な脱酸素能力を示す脱酸素組成物を提供するという驚くべき事実に基づいてなされたものである。さらに、該共重合体は透明性に優れ、且つ水蒸気透過率が低いという特徴をも付与する。
未置換または置換ノルボルネン化合物ユニットを有する分子量が１０００ないし１００００のオリゴマーが酸素捕捉性ポリマーとして公知であるが、この場合には酸素反応点はオリゴマー末端に存在する炭素−炭素二重結合である点で本発明と本質的に異なる。
The present invention relates to (i) at least one (a) ethylene unit and (b) an unsubstituted or substituted norbornene compound in a more distorted structure by connecting and constraining carbon atoms constituting a cyclic alkylene skeleton. The cyclic olefin copolymer composed of units is combined with (ii) a transition metal catalyst, (iii) optionally a photoinitiator, and (iv) optionally a polymer diluent to provide a high degree of processability and packaging material. Has sufficient compatibility with common polymers used in forming and exhibits significant deoxygenation ability either alone or as part of a film or article used to package oxygen sensitive products This is based on the surprising fact of providing a deoxygenating composition. Furthermore, the copolymer imparts the characteristics of excellent transparency and low water vapor transmission rate.
Oligomers having an unsubstituted or substituted norbornene compound unit and a molecular weight of 1000 to 10,000 are known as oxygen scavenging polymers. In this case, the oxygen reaction point is a carbon-carbon double bond existing at the end of the oligomer. Essentially different from the present invention.
すなわち、本発明は、下記一般式（１）で表される（i）少なくとも１つの（ａ）エチレンユニットと（ｂ）未置換または置換ノルボルネン化合物ユニットから構成される環状オレフィン共重合体、（ii）遷移金属触媒、（iii）任意に光開始剤、及び（iv）任意にポリマー希釈剤を含む脱酸素組成物に関する。
本発明によって、高度の加工性、及び包装材料を形成する際に使用される一般的ポリマーへの十分な相容性を持ち、単独でも、または酸素感受性製品を包装するために使用されるフィルムまたは物品の一部としても有意な脱酸素能力を示す工業的に有用な脱酸素組成物を提供する。 According to the present invention, a film or a film having a high degree of processability and sufficient compatibility with common polymers used in forming packaging materials, either alone or for packaging oxygen sensitive products Provided are industrially useful deoxygenation compositions that exhibit significant deoxygenation capability as part of an article.
以下、本発明に関わる脱酸素組成物について詳細に説明する。
本発明の脱酸素組成物は、下記一般式（１）で表される少なくとも１つの（ａ）エチレンユニットと（ｂ）未置換または置換ノルボルネン化合物ユニットから構成される環状オレフィン共重合体を１つ以上含む。
The deoxygenated composition of the present invention includes one cyclic olefin copolymer composed of at least one (a) ethylene unit represented by the following general formula (1) and (b) an unsubstituted or substituted norbornene compound unit. Including above.
本発明で使用できる未置換または置換ノルボルネン化合物ユニットとしては、下記一般式（２）で表すことができる。
ハロゲンを含む置換基としては具体的には、例えば、弗素、塩素、臭素、ヨウ素等のハロゲン基、クロロメチル基、ブロモメチル基、クロロエチル基等の炭素数１〜２０のハロゲン置換アルキル基等を挙げることができる。
酸素を含む置換基として具体的には、メトキシ基、エトキシ基、プロポキシ基、フェノキシ基等の炭素数１〜２０のアルコキシ基、メトキシカルボニル基、エトキシカルボニル基等の炭素数１〜２０のアルコキシカルボニル基等を挙げることができる。
窒素原子を含む置換基としては具体的には、例えば、ジメチルアミノ基、ジエチルアミノ基等の炭素数１〜２０のアルキルアミノ基やシアノ基等を挙げることができる。
Specific examples of the substituent containing halogen include halogen groups such as fluorine, chlorine, bromine and iodine, halogen substituted alkyl groups having 1 to 20 carbon atoms such as chloromethyl group, bromomethyl group and chloroethyl group. be able to.
Specific examples of the substituent containing oxygen include alkoxy groups having 1 to 20 carbon atoms such as methoxy group, ethoxy group, propoxy group, and phenoxy group, and alkoxycarbonyls having 1 to 20 carbon atoms such as methoxycarbonyl group and ethoxycarbonyl group. Groups and the like.
Specifically as a substituent containing a nitrogen atom, C1-C20 alkylamino groups, such as a dimethylamino group and a diethylamino group, a cyano group, etc. can be mentioned, for example.
前記一般式（２）で表される環状オレフィンの具体例としては、ビシクロ［２．２．１］ヘプト−２−エン（以下「ノルボルネン」と称する）、５−メチルノルボルネン、５−エチルノルボルネン、５−プロピルノルボルネン、５，６−ジメチルノルボルネン、１−メチルノルボルネン、７−メチルノルボルネン、５，５，６−トリメチルノルボルネン、５−フェニルノルボルネン、５−ベンジルノルボルネン、５−エチリデンノルボルネン、５−ビニルノルボルネン、５−クロロノルボルネン、５−シアノノルボルネン、５−フルオロノルボルネン、５，５−ジクロロノルボルネン、５，５，６−トリフルオロノルボルネン、５−メトキシノルボルネン、５−ジメチルアミノノルボルネン、５，５，６−トリフルオロ−６−メチルノルボルネン、トリシクロ［４．３．０．１2.5］−３−デセン、トリシクロ［４．４．０．１2.5］−３−ウンデセン、テトラシクロ［４．４．０．１2.5．１7.10］−３−ドデセン、８−メチルテトラシクロ［４．４．０．１2.5．１7.10］−３−ドデセン、８−エチルテトラシクロ［４．４．０．１2.5．１7.10］−３−ドデセン、８−プロピルテトラシクロ［４．４．０．１2.5．１7.10］−３−ドデセン、８−ブチルテトラシクロ［４．４．０．１2.5．１7.10］−３−ドデセン、８−イソブチルテトラシクロ［４．４．０．１2.5．１7.10］−３−ドデセン、 Specific examples of the cyclic olefin represented by the general formula (2) include bicyclo [2.2.1] hept-2-ene (hereinafter referred to as “norbornene”), 5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5,6-dimethylnorbornene, 1-methylnorbornene, 7-methylnorbornene, 5,5,6-trimethylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene, 5-ethylidenenorbornene, 5-vinylnorbornene , 5-chloronorbornene, 5-cyanonorbornene, 5-fluoronorbornene, 5,5-dichloronorbornene, 5,5,6-trifluoronorbornene, 5-methoxynorbornene, 5-dimethylaminonorbornene, 5,5,6- Trifluoro-6-methylnorbol Emissions, tricyclo [4.3.0.1 2.5] -3- decene, tricyclo [4.4.0.1 2.5] -3- undecene, tetracyclo [4.4.0.1 2.5. 1 7.10 ] -3-dodecene, 8-methyltetracyclo [4.4.0.1 2.5 . 1 7.10 ] -3-dodecene, 8-ethyltetracyclo [4.4.0.1 2.5 . 1 7.10] -3-dodecene, 8-propyl-tetracyclo [4.4.0.1 2.5. 1 7.10 ] -3-dodecene, 8-butyltetracyclo [4.4.0.1 2.5 . 1 7.10 ] -3-dodecene, 8-isobutyltetracyclo [4.4.0.1 2.5 . 1 7.10 ] -3-dodecene,
８−エチリデンテトラシクロ［４．４．０．１2.5．１7.10］−３−ドデセン、８−クロロテトラシクロ［４．４．０．１2.5．１7.10］−３−ドデセン、８−シアノテトラシクロ［４．４．０．１2.5．１7.10］−３−ドデセン、８−フルオロテトラシクロ［４．４．０．１2.5．１7.10］−３−ドデセン、８，８−ジクロロテトラシクロ［４．４．０．１2.5．１7.10］−３−ドデセン、８−メトキシテトラシクロ［４．４．０．１2.5．１7.10］−３−ドデセン、８−ジメチルアミノテトラシクロ［４．４．０．１2.5．１7.10］−３−ドデセン、８，８，９−トリフルオロテトラシクロ［４．４．０．１2.5．１7.10］−３−ドデセン、８，８，９−トリフルオロ−９−メチルテトラシクロ［４．４．０．１2.5．１7.10］−３−ドデセン、ペンタシクロ［６．５．１．１3.6．０2.7．０9.13］−４−ペンタデセン、ペンタシクロ［６．６．１．１3.6．０2.7．０9.14］−４−ヘキサデセン、ヘキサシクロ［６．６．１．１3.6．１10.13．０2.7．０9.14］−４−ヘプタデセン等が例示される。これらの環状オレフィンは１種単独又は２種以上組み合わせて用いることが出来る。これらの環状オレフィンのなかで、ノルボルネン、トリシクロ［４．３．０．１2.5］−３−デセン、トリシクロ［４．４．０．１2.5］−３−ウンデセン、テトラシクロ［４．４．０．１2.5．１7.10］−３−ドデセンが好ましく、特にノルボルネンが好ましい。 8-ethylidenetetracyclo [4.4.0.1 2.5 . 1 7.10 ] -3-dodecene, 8-chlorotetracyclo [4.4.0.1 2.5 . 1 7.10 ] -3-dodecene, 8-cyanotetracyclo [4.4.0.1 2.5 . 1 7.10 ] -3-dodecene, 8-fluorotetracyclo [4.4.0.1 2.5 . 1 7.10 ] -3-dodecene, 8,8-dichlorotetracyclo [4.4.0.1 2.5 . 1 7.10 ] -3-dodecene, 8-methoxytetracyclo [4.4.0.1 2.5 . 1 7.10 ] -3-dodecene, 8-dimethylaminotetracyclo [4.4.0.1 2.5 . 1 7.10 ] -3-dodecene, 8,8,9-trifluorotetracyclo [4.4.0.1 2.5 . 1 7.10 ] -3-dodecene, 8,8,9-trifluoro-9-methyltetracyclo [4.4.0.1 2.5 . 1 7.10 ] -3-dodecene, pentacyclo [6.5.1.1 3.6 . 0 2.7 . 0 9.13 ] -4-pentadecene, pentacyclo [6.6.1.1 3.6 . 0 2.7 . 0 9.14] -4-hexadecene, hexacyclo [6.6.1.1 3.6. 1 10.13 . 0 2.7 . 0 9.14] -4-heptadecene, and the like. These cyclic olefins can be used alone or in combination of two or more. Among these cyclic olefins, norbornene, tricyclo [4.3.0.1 2.5 ] -3-decene, tricyclo [4.4.0.1 2.5 ] -3-undecene, tetracyclo [4.4.0. 1 2.5 . 17.10 ] -3-dodecene is preferred, and norbornene is particularly preferred.
本発明には、本発明のポリマー成分の未置換または置換ノルボルネン化合物ユニットから誘導される脱酸素性及び他のソースから誘導される脱酸素性の組合せも含まれる。これらの組合せは、本発明のポリマー成分を以下に詳記するように脱酸素性を有する１つ以上の追加のポリマー成分とブレンドすることにより、または本発明のポリマー成分に脱酸素性を与える追加のモノマー単位を配合することにより達成される。
例えば、本発明のポリマー成分をエチレン不飽和炭素−炭素二重結合を有するモノマー単位と併用することにより、酸素反応のための更なる別のサイトが得られる。該モノマー単位は通常非共役ジエンとして特徴付けられ、例えば、オクタジエン、ヘキサジエン、ジシクロペンタジエン、エチリデンノルボルネン、ビニルノルボルネン等が挙げられる。
The present invention also includes a combination of deoxygenation derived from unsubstituted or substituted norbornene compound units of the polymer component of the present invention and deoxygenation derived from other sources. These combinations can be added by blending the polymer component of the present invention with one or more additional polymer components having deoxygenating properties, as detailed below, or by adding deoxygenating properties to the polymer component of the present invention. This is achieved by blending the monomer units.
For example, by using the polymer component of the present invention in combination with a monomer unit having an ethylenically unsaturated carbon-carbon double bond, still another site for oxygen reaction is obtained. The monomer unit is usually characterized as a non-conjugated diene, and examples thereof include octadiene, hexadiene, dicyclopentadiene, ethylidene norbornene, vinyl norbornene and the like.
ポリマー成分は、フィルムまたは他の好適な包装材料、例えば、バッグまたはパウチ、に形成され得る。前記ポリマー成分はフィルム、即ち、このフィルムが例えばガスバリヤー層、シール層等を有する多層フィルムであるところの１つ以上の層を形成するための単一ポリマー材料として使用され得、他の脱酸素性ポリマー物質、例えば、ポリブタジエン、とブレンドされ、または包装フィルム材料の形成に有用であるとして公知であり且つしばしば得られたフィルムをより可撓性及び／又は加工性とし得る１つ以上の希釈剤ポリマーとブレンドされる。好適な希釈剤ポリマーには、例えば、低密度ポリエチレン、極低密度ポリエチレン、超低密度ポリエチレン、高密度ポリエチレン及び線状低密度ポリエチレン等のポリエチレン、例えば、ポリエチレンテレフタレート（ＰＥＴ）等のポリエステル、ポリ塩化ビニル（ＰＶＣ）、ポリ塩化ビニリデン（ＰＶＤＣ）、エチレンコポリマー（例えば、エチレン／酢酸ビニルコポリマー、エチレン／アルキル（メタ）アクリレートコポリマー、エチレン／（メタ）アクリル酸コポリマー）、アイオノマーが含まれるが、これらに限定されない。異なる希釈剤ポリマーのブレンドも使用し得る。 The polymer component can be formed into a film or other suitable packaging material, such as a bag or pouch. The polymer component can be used as a single polymer material to form a film, ie, one or more layers where the film is a multilayer film having, for example, a gas barrier layer, a seal layer, etc. One or more diluents that are blended with a functional polymeric material, such as polybutadiene, or that are known to be useful in forming packaging film materials and that can often make the resulting film more flexible and / or processable Blended with polymer. Suitable diluent polymers include, for example, low density polyethylene, very low density polyethylene, ultra low density polyethylene, high density polyethylene and linear low density polyethylene, such as polyesters such as polyethylene terephthalate (PET), polychlorinated These include vinyl (PVC), polyvinylidene chloride (PVDC), ethylene copolymers (eg, ethylene / vinyl acetate copolymers, ethylene / alkyl (meth) acrylate copolymers, ethylene / (meth) acrylic acid copolymers), ionomers, It is not limited. Blends of different diluent polymers can also be used.
通常、前記希釈剤ポリマーは半結晶性材料である。有利には、本発明の組成物のポリマー成分は未置換及び置換ノルボルネン化合物ユニット含量に依存して結晶性から非晶性であり、前記希釈剤ポリマーと十分に相容性である。未置換及び置換ノルボルネンの含量は少なくとも０．１ｍｏｌ％であるが９９．９ｍｏｌ％未満であり、好ましくは６５ｍｏｌ％未満であり、より好ましくは３５ｍｏｌ％から５０ｍｏｌ％の範囲であるが、必ずしもこれらに限定されない。特定の希釈剤ポリマーの選択は製造しようとする物品及びその最終用途にかなり依存する。例えば、製造した物品の透明性、清浄性、バリヤー性、機械的特性及び／又はテキスチャーを与えるようなある種のポリマーは当業者に公知である。 Usually, the diluent polymer is a semi-crystalline material. Advantageously, the polymer component of the composition of the present invention is crystalline to amorphous depending on the content of unsubstituted and substituted norbornene compound units and is sufficiently compatible with the diluent polymer. The content of unsubstituted and substituted norbornene is at least 0.1 mol% but less than 99.9 mol%, preferably less than 65 mol%, more preferably in the range of 35 mol% to 50 mol%, but not necessarily limited thereto Not. The selection of a particular diluent polymer is highly dependent on the article to be manufactured and its end use. For example, certain polymers are known to those skilled in the art that provide the transparency, cleanliness, barrier properties, mechanical properties and / or texture of the manufactured article.
ポリマー成分と一緒に、本発明の脱酸素組成物は脱酸素剤触媒として遷移金属化合物を含む。遷移金属触媒は、周期表の第１、第２または第３遷移元素系列から選択される金属を含む塩である。金属は、好ましくはＲｈ、Ｒｕ、またはＳｃ−Ｃｕ系列（すなわち、Ｓｃ、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ及びＣｕ）元素の１つであり、より好ましくはＭｎ、Ｆｅ、Ｃｏ、Ｎｉ及びＣｕの少なくとも１つ、最も好ましくはＣｏである。前記塩に対する好適なアニオンには、塩素、酢酸、オレイン酸、ステアリン酸、パルミチン酸、２−エチルヘキサン酸、ネオデカン酸及びナフテン酸アニオンが含まれるが、これらに限定されない。代表的な塩には２−エチルヘキサン酸コバルト（ＩＩ）、オレイン酸コバルト及びネオデカン酸コバルト（ＩＩ）が含まれる。金属塩はアイオノマーであってもよく、この場合ポリマー対イオンが使用される。包装物品を形成する際に使用する場合、本発明の脱酸素組成物は上記ポリマー及び遷移金属触媒のみを含む。しかしながら、更に脱酸素性の開始を促進し、コントロールするために光開始剤を添加することができる。脱酸素組成物に光開始剤またはそのブレンドを添加することが好ましく、酸化防止剤が加工及び貯蔵中の組成物の早期酸化を防止するために添加されているときには特に好ましい。光開始剤を含有する脱酸素組成物に所望の時期に光を照射することにより、酸素との反応の開始が促進されて、脱酸素組成物の酸素掃去の誘導期が減少または消失し、その結果、脱酸素組成物の酸素掃去機能を速やかに発現することが可能となる。 Along with the polymer component, the oxygen scavenging composition of the present invention includes a transition metal compound as a scavenger catalyst. The transition metal catalyst is a salt containing a metal selected from the first, second or third transition element series of the periodic table. The metal is preferably one of the Rh, Ru, or Sc—Cu series (ie, Sc, Ti, V, Cr, Mn, Fe, Co, Ni and Cu) elements, more preferably Mn, Fe, Co. , Ni and Cu, and most preferably Co. Suitable anions for the salt include, but are not limited to, chlorine, acetic acid, oleic acid, stearic acid, palmitic acid, 2-ethylhexanoic acid, neodecanoic acid and naphthenic acid anions. Exemplary salts include cobalt (II) 2-ethylhexanoate, cobalt oleate and cobalt (II) neodecanoate. The metal salt may be an ionomer, in which case a polymer counter ion is used. When used in forming a packaged article, the oxygen scavenging composition of the present invention comprises only the polymer and a transition metal catalyst. However, a photoinitiator can be added to further promote and control deoxygenation initiation. It is preferred to add a photoinitiator or blend thereof to the deoxygenated composition, especially when an antioxidant is added to prevent premature oxidation of the composition during processing and storage. By irradiating the deoxygenated composition containing the photoinitiator with light at a desired time, the initiation of the reaction with oxygen is promoted, and the induction period of oxygen scavenging of the deoxygenated composition is reduced or eliminated, As a result, the oxygen scavenging function of the deoxygenated composition can be rapidly expressed.
好適な光開始剤は当業者に公知である。好適な光開始剤としては、ベンゾフェノン及びその誘導体、例えば、メトキシベンゾフェノン、ジメトキシベンゾフェノン、ジメチルベンゾフェノン、ジフェノキシベンゾフェノン、アリルオキシベンゾフェノン、ジアリルオキシベンゾフェノン、ドデシルオキシベンゾフェノン、ジベンゾスベロン、４，４’−ビス（４−イソプロピルフェノキシ）ベンゾフェノン、４−モルホリノベンゾフェノン、４−アミノベンゾフェノン、トリベンゾイルトリフェニルベンゼン、トリトルオイルトリフェニルベンゼン、４，４’−ビス（ジメチルアミノ）ベンゾフェノン；アセトフェノン及びその誘導体、例えば、ｏ−メチルアセトフェノン、４’−メトキシアセトフェノン、バレロフェノン、ヘキサノフェノン、α−フェニル−ブチロフェノン、ｐ−モルホリノプロピオフェノン；ベンゾイン及びその誘導体、例えば、ベンゾインメチルエーテル、ベンゾインブチルエーテル、ベンゾインテトラヒドロピラニルエーテル、４−ｏ−モルホリノデオキシベンゾイン； Suitable photoinitiators are known to those skilled in the art. Suitable photoinitiators include benzophenone and its derivatives such as methoxybenzophenone, dimethoxybenzophenone, dimethylbenzophenone, diphenoxybenzophenone, allyloxybenzophenone, diallyloxybenzophenone, dodecyloxybenzophenone, dibenzosuberone, 4,4′-bis (4-Isopropylphenoxy) benzophenone, 4-morpholinobenzophenone, 4-aminobenzophenone, tribenzoyltriphenylbenzene, tritoluoyltriphenylbenzene, 4,4′-bis (dimethylamino) benzophenone; acetophenone and its derivatives, such as o-methylacetophenone, 4′-methoxyacetophenone, valerophenone, hexanophenone, α-phenyl-butyrophenone, p Morpholino propiophenone; benzoin and its derivatives, e.g., benzoin methyl ether, benzoin butyl ether, benzoin tetrahydropyranyl ether, 4-o-morpholino deoxybenzoin;
置換及び未置換アントラキノン、α−テトラロン、アセナフテンキノン、９−アセチルフェナントレン、２−アセチルフェナントレン、１０−チオキサンテノン、３−アセチルフェナントレン、３−アセチルインドール、９−フルオレノン、１−インダノン、１，３，５−トリアセチルベンゼン、チオキサンテン−９−オン、イソプロピルチオキサンテン−９−オン、キサンテン−９−オン、７−Ｈ−ベンゾ［ｄｅ］アントラセン−７−オン、１’−アセトナフトン、２’−アセトナフトン、アセトナフトン、ベンゾ［ａ］アントラセン−７，１２−ジオン、２，２−ジメトキシ−２−フェニルアセトフェノン、α，α−ジエトキシアセトフェノン、α，α−ジブトキシアセトフェノン、４−ベンゾイル−４’−メチル（ジフェニルスルフィド）等が含まれるが、これらに限定されない。 Substituted and unsubstituted anthraquinone, α-tetralone, acenaphthenequinone, 9-acetylphenanthrene, 2-acetylphenanthrene, 10-thioxanthenone, 3-acetylphenanthrene, 3-acetylindole, 9-fluorenone, 1-indanone, 1,3 5-triacetylbenzene, thioxanthen-9-one, isopropylthioxanthen-9-one, xanthen-9-one, 7-H-benzo [de] anthracen-7-one, 1'-acetonaphthone, 2'-acetonaphthone , Acetonaphthone, benzo [a] anthracene-7,12-dione, 2,2-dimethoxy-2-phenylacetophenone, α, α-diethoxyacetophenone, α, α-dibutoxyacetophenone, 4-benzoyl-4′-methyl (Diphenyl sulfide) Etc., but is not limited to these.
一重項酸素発生性光増感剤（例えば、ローズベンガル、メチレンブルー及びテトラフェニルポルフィン）及びポリマー開始剤（例えば、ポリ（エチレン−一酸化炭素）及びオリゴ［２−ヒドロキシ−２−メチル−１−［４−（１−メチルビニル）フェニル］プロパノン］）も使用し得る。しかしながら、光開始剤は通常より迅速且つより効率的な開始を与えるので好ましい。化学線を使用するときにはより長い波長で開始し得る。なぜならば、長波長は発生させるのにより安価であり且つ短い波長よりも有害な副作用が少ないからである。
光開始剤を存在させるときには、光開始剤は放射線に曝したときに本発明の組成物による脱酸素の開始を強化及び／又は促進し得る。使用する光開始剤の最適量はポリマー中に存在する未置換及び置換ノルボルネン化合物ユニットから誘導されるモノマー単位の量及び種類、使用する放射線の波長及び強度、使用する酸化防止剤の種類及び量、並びに使用する光開始剤の種類に依存する。光開始剤の量は脱酸素組成物の使用方法にも依存し得る。例えば、光開始剤含有組成物が使用する放射線に対してやや不透過性である他の層をその下に含むフィルム層中に存在するならば、より多くの開始剤が必要とされる。しかしながら、多くの用途のために使用される光開始剤の量は組成物の全量の０．０１〜１０重量％である。脱酸素は、下記するように本発明の組成物を含む物品を化学線または電子ビーム線に曝すことにより開始され得る。
Singlet oxygen-generating photosensitizers (eg, rose bengal, methylene blue and tetraphenylporphine) and polymer initiators (eg, poly (ethylene-carbon monoxide) and oligo [2-hydroxy-2-methyl-1- [ 4- (1-methylvinyl) phenyl] propanone]) may also be used. However, photoinitiators are preferred because they usually provide a faster and more efficient initiation. When using actinic radiation, one can start with longer wavelengths. This is because long wavelengths are cheaper to generate and have fewer harmful side effects than short wavelengths.
When present, the photoinitiator can enhance and / or promote the initiation of deoxygenation by the composition of the present invention when exposed to radiation. The optimal amount of photoinitiator used is the amount and type of monomer units derived from unsubstituted and substituted norbornene compound units present in the polymer, the wavelength and intensity of radiation used, the type and amount of antioxidant used, As well as the type of photoinitiator used. The amount of photoinitiator can also depend on the method of use of the oxygen scavenging composition. For example, more initiator is needed if it is present in a film layer that underlies other layers that are somewhat opaque to the radiation used by the photoinitiator-containing composition. However, the amount of photoinitiator used for many applications is from 0.01 to 10% by weight of the total composition. Deoxygenation can be initiated by exposing an article comprising the composition of the present invention to actinic or electron beam radiation as described below.
配合及びフィルム形成中の成分の劣化を遅らすために１つ以上の酸化防止剤を本発明の脱酸素組成物に配合し得る。前記酸化防止剤は照射の非存在下で脱酸素活性が発揮される誘導期間を延長させるが、脱酸素性が要求されるときに層または物品、及び配合した光開始剤、に放射線を暴露させることができる。好適な酸化防止剤には、２，６−ジ（ｔ−ブチル）−４−メチルフェノール（ＢＨＴ）、２，２’−メチレン−ビス（６−ｔ−ブチル−ｐ−クレゾール）、トリフェニルホスファイト、トリス−（ノニルフェニル）ホスファイト、ジラウリルチオジプロピンネート等が含まれる。
酸化防止剤を本発明の組成物の一部として配合するとき、該酸化防止剤は好ましくは脱酸素組成物の成分及び生じたブレンド中に存在する他の物質が配合及び加工中に酸化されるのを防止する量で存在する。しかしながら、その量は脱酸素が開始した後生じた層、フィルムまたは物品の脱酸素活性を妨害する量未満であることが好ましい。所与の組成物での必要量は該組成物中に存在する成分、使用する特定酸化防止剤、成形物品を形成するために使用される熱加工の程度及び量、並びに脱酸素を開始するために適用される放射線の量及び波長に依存する。通常、酸化防止剤は組成物の全量の０．０１〜１重量％の量で使用される。
One or more antioxidants may be incorporated into the oxygen scavenging composition of the present invention to delay component degradation during compounding and film formation. The antioxidant extends the induction period during which deoxygenation activity is exerted in the absence of irradiation, but exposes the layer or article and the formulated photoinitiator to radiation when deoxygenation is required be able to. Suitable antioxidants include 2,6-di (t-butyl) -4-methylphenol (BHT), 2,2′-methylene-bis (6-t-butyl-p-cresol), triphenylphosphine. Phyto, tris- (nonylphenyl) phosphite, dilauryl thiodipropinate and the like are included.
When an antioxidant is formulated as part of the composition of the present invention, the antioxidant is preferably oxidized during formulation and processing of the components of the oxygen scavenging composition and other materials present in the resulting blend. Present in an amount that prevents However, it is preferred that the amount be less than an amount that interferes with the deoxygenation activity of the layer, film or article that results after deoxygenation has begun. The required amount for a given composition is the components present in the composition, the specific antioxidant used, the degree and amount of thermal processing used to form the molded article, and to initiate deoxygenation. Depending on the amount and wavelength of radiation applied. Usually, the antioxidant is used in an amount of 0.01 to 1% by weight of the total amount of the composition.
本発明の脱酸素組成物中に配合され得る他の添加剤には、充填剤、顔料、染料、安定剤、加工助剤、可塑剤、難燃剤、防曇剤、粘着防止剤等が含まれるが、必ずしもこれらに限定されない。
本発明の脱酸素組成物中に使用される成分の量により、該組成物の用途及び有効性が影響される。すなわち、ポリマー、遷移金属触媒、並びに任意の光開始剤、酸化防止剤、ポリマー希釈剤、添加剤等の量は所望の物品及びその最終用途に応じて変更し得る。例えば、上記ポリマーの主な機能の１つは脱酸素中酸素と不可逆的に反応することであり、遷移金属触媒の主な機能はこのプロセスを促進することである。よって、存在するポリマーの量は組成物の脱酸素能力、即ち、組成物が消費し得る酸素の量、にかなり影響を及ぼし、遷移金属触媒の量は酸素消費率及び誘導期間に影響を及ぼす。
Other additives that can be incorporated into the oxygen scavenging composition of the present invention include fillers, pigments, dyes, stabilizers, processing aids, plasticizers, flame retardants, antifogging agents, anti-tacking agents, and the like. However, it is not necessarily limited to these.
The amount of ingredients used in the oxygen scavenging composition of the present invention affects the use and effectiveness of the composition. That is, the amount of polymer, transition metal catalyst, and any photoinitiator, antioxidant, polymer diluent, additive, etc. can be varied depending on the desired article and its end use. For example, one of the main functions of the polymer is to react irreversibly with oxygen during deoxygenation, and the main function of the transition metal catalyst is to facilitate this process. Thus, the amount of polymer present significantly affects the deoxygenation capacity of the composition, i.e., the amount of oxygen that the composition can consume, and the amount of transition metal catalyst affects the oxygen consumption rate and induction period.
本発明の組成物は、慣用されているエチレン不飽和ポリマーを含む組成物に対比して良好な加工性及び相容性を有していながら、所望の率及び能力で脱酸素性を示すことができる。よって、本発明の組成物は、それ自体または希釈剤フィルム形成性ポリマー、例えば、ポリオレフィン等、とのブレンドとして容易に製造、加工され得る包装材料またはフィルムを形成するために使用することができる。更に、本発明の脱酸素組成物は、パッケージに収容されている製品の色、味及び／又は臭いを実質的に損なうことなくパッケージキャビティ内の酸素を消費、欠乏させると考えられる。
本発明の組成物中に含有されるポリマー成分の量は、組成物または該組成物から形成される層の１〜１００重量％、好ましくは５〜９７．５重量％、より好ましくは１０〜９５重量％、一層好ましくは１５〜９２．５重量％、更に好ましくは２０〜９０重量％の範囲である。典型的には、遷移金属触媒の量は金属含量のみ（リガンド、対イオン等を除く）に基づいて脱酸素組成物の０．００１〜１重量％である。１つ以上の他の脱酸素化合物及び／又は希釈剤ポリマーを組成物の一部として使用するときには、前記した他の材料は脱酸素組成物の９９重量％くらい多くの量、好ましくは最高７５重量％を占め得る。通常使用される他の添加剤は脱酸素組成物の１０重量％以下、好ましくは５重量％以下しか占めない。
The compositions of the present invention may exhibit deoxidation at the desired rate and capacity while having good processability and compatibility compared to compositions containing conventional ethylenically unsaturated polymers. it can. Thus, the compositions of the present invention can be used to form packaging materials or films that can be readily manufactured and processed as such or as blends with diluent film forming polymers such as polyolefins. Furthermore, the oxygen scavenging composition of the present invention is believed to consume and deplete oxygen within the package cavity without substantially compromising the color, taste and / or odor of the product contained in the package.
The amount of the polymer component contained in the composition of the present invention is 1 to 100% by weight of the composition or a layer formed from the composition, preferably 5 to 97.5% by weight, more preferably 10 to 95%. % By weight, more preferably 15 to 92.5% by weight, and still more preferably 20 to 90% by weight. Typically, the amount of transition metal catalyst is 0.001-1% by weight of the deoxygenated composition based on the metal content alone (excluding ligands, counterions, etc.). When one or more other deoxygenating compounds and / or diluent polymers are used as part of the composition, the other materials mentioned are in amounts as high as 99% by weight of the deoxygenating composition, preferably up to 75%. % Can be accounted for. Other commonly used additives comprise no more than 10%, preferably no more than 5% by weight of the oxygen scavenging composition.
本発明の脱酸素組成物は、通常の脱酸素組成物では達成し得ない優れた性質を有し得る。ポリマー成分は高含量の未置換及び置換ノルボルネン化合物ユニットを含む、すなわち、高い脱酸素能力を有する。包装用途に好適なフィルムは、ポリマー／遷移金属組成物から直接形成される。更に、本発明の組成物は、該組成物が希釈剤ポリマーを含んでいるときでも高含量のポリマー脱酸素成分を含む。上記したように、前記ポリマーは公知のフィルム形成性ポリマー、例えば、ポリオレフィン、特にフィルム包装物品を形成する際に通常使用されている半結晶性ポリマーと十分に相容性である。この高い相容性のために、ポリマー及び他の希釈剤ポリマーは任意の比で容易にブレンドされる。対照的に、従来使用されている非晶質エチレン不飽和ポリマーではフィルム等に加工、例えば、押出し加工、するのに適した高含量ブレンドが容易には得られない。 The oxygen scavenging composition of the present invention may have excellent properties that cannot be achieved with a normal oxygen scavenging composition. The polymer component contains a high content of unsubstituted and substituted norbornene compound units, i.e. has a high deoxygenation capacity. Films suitable for packaging applications are formed directly from polymer / transition metal compositions. In addition, the compositions of the present invention include a high content of polymer deoxygenation components even when the composition includes a diluent polymer. As noted above, the polymer is sufficiently compatible with known film-forming polymers, such as polyolefins, particularly semi-crystalline polymers commonly used in forming film-wrapped articles. Because of this high compatibility, the polymer and other diluent polymers are easily blended in any ratio. In contrast, conventionally used amorphous ethylenically unsaturated polymers do not readily provide high content blends suitable for processing into films and the like, such as extrusion.
本発明の組成物は高速で所望の特性、例えば高い透明性、高い押出量でも少ない表面欠陥等を有するフィルムまたはフィルム層に容易に、例えば、押出し加工等の加工に供される。
上記したように、本発明の組成物は、脱酸素単層フィルム、多層フィルムの脱酸素層または各種包装用途の他の物品を作成するために使用される。単層物品は押出し加工により容易に製造される。多層フィルムは、共押出し、コーティング、ラミネーションまたは押出し／ラミネーション等を用いて製造される。多層物品の追加層の少なくとも１つは、２５℃で５．８×１０-8ｃｍ3／ｍ2・ｓ・Ｐａ（５００ｃｍ3／ｍ2・２４時間・ａｔｍ）以下の酸素透過率を有する材料を含み得る。該酸素バリヤー層に通常使用されるポリマーには、ポリ（エチレン／ビニルアルコール）、ポリ（ビニルアルコール）、ポリアクリロニトリル、ＰＶＣ、ＰＶＤＣ、ＰＥＴ、高バリヤーシリコーンまたは酸化アルミニウム層（例えば、ＳｉＯx）、及びポリアミド（例えば、ナイロン６、ＭＸＤ６、ナイロン６６及び各種アミドコポリマー）が含まれる。金属ホイル層も酸素バリヤー性を与え得る。
The composition of the present invention is easily subjected to processing such as extrusion processing at a high speed to a film or film layer having desired characteristics such as high transparency and a small surface defect even at a high extrusion rate.
As noted above, the compositions of the present invention are used to make deoxygenated monolayer films, deoxygenated layers of multilayer films or other articles for various packaging applications. Single layer articles are easily manufactured by extrusion. Multilayer films are manufactured using coextrusion, coating, lamination, extrusion / lamination, and the like. At least one of the additional layers of the multilayer article is a material having an oxygen transmission rate at 25 ° C. of 5.8 × 10 −8 cm 3 / m 2 · s · Pa (500 cm 3 / m 2 · 24 hours · atm) or less. Can be included. Polymers commonly used for the oxygen barrier layer include poly (ethylene / vinyl alcohol), poly (vinyl alcohol), polyacrylonitrile, PVC, PVDC, PET, high barrier silicone or aluminum oxide layers (eg, SiO x ), And polyamides such as nylon 6, MXD6, nylon 66 and various amide copolymers. The metal foil layer can also provide oxygen barrier properties.
他の追加層には、１つ以上の酸素透過性層が含まれる。１つの好ましい包装構造、特に食品用可撓性パッケージでは、層は、パッケージの外側からパッケージの最内層に向かって、（ａ）酸素バリヤー層、（ｂ）脱酸素層、すなわち上記した脱酸素組成物を含む層、及び任意に（ｃ）酸素透過性層を含む。層（ａ）の酸素バリヤー性をコントロールすると、脱酸素層（ｂ）への酸素進入率を制限して脱酸素能力の消耗率を抑えることによりパッケージの脱酸素寿命が調節される。層（ｃ）の酸素透過率をコントロールすると、脱酸素層（ｂ）の組成に関係なく全構造についての脱酸素率の上限が設定される。
これは、パッケージをシールする前の空気の存在下でのフィルムの取り扱い寿命を延長させるのに役立つ。更に、層（ｃ）は脱酸素層の各成分または副生成物のパッケージの内部への移行に対するバリヤーとなる。「内部への露出」は、酸素感受性製品が収容されている内部キャビティに直接、またはＯ2透過性である層を介して間接的に接する脱酸素組成物を含む包装物品の一部を指す。更に、層（ｃ）はまた多層フィルムのヒートシール性、透明性及び／又は粘着防止性を改善する。結合（ｔｉｅ）層のような追加の層を使用することができる。この結合層に通常使用されるポリマーには、例えば酸無水物官能化ポリオレフィンが含まれる。
Other additional layers include one or more oxygen permeable layers. In one preferred packaging structure, particularly a food flexible package, the layers are from the outside of the package towards the innermost layer of the package: (a) an oxygen barrier layer, (b) a deoxygenation layer, ie the deoxygenation composition described above. A layer containing matter, and optionally (c) an oxygen permeable layer. When the oxygen barrier property of the layer (a) is controlled, the deoxidation life of the package is adjusted by limiting the oxygen penetration rate into the deoxygenation layer (b) and thereby suppressing the consumption rate of the deoxygenation capacity. When the oxygen transmission rate of the layer (c) is controlled, the upper limit of the deoxygenation rate for the entire structure is set regardless of the composition of the deoxidation layer (b).
This helps to extend the handling life of the film in the presence of air prior to sealing the package. In addition, layer (c) provides a barrier to the migration of each component or by-product of the deoxygenation layer into the package. “External exposure” refers to a portion of a packaging article that includes a deoxygenating composition that directly contacts an internal cavity containing an oxygen sensitive product or indirectly through a layer that is O 2 permeable. Furthermore, layer (c) also improves the heat sealability, transparency and / or anti-stick properties of the multilayer film. Additional layers such as tie layers can be used. Polymers commonly used for this tie layer include, for example, acid anhydride functionalized polyolefins.
本発明は、各種製品、化合物、組成物、コーティング等を作成するために使用され得る。２つの好ましい形態は、いずれも食品または非食品を包装するのに有用であるシーリング化合物及び可撓性フィルムである。
上記した応用のすべてにおいて、（ａ）エチレンユニットと（ｂ）未置換または置換ノルボルネン化合物ユニットから構成される環状オレフィン共重合体及び遷移金属触媒を使用することにより、脱酸素反応の望ましくない副生成物を抑制しながら容器の内部環境から酸素を効果的に除去し得る。
本発明の方法は、酸素感受性製品を収容しているパッケージキャビティに上記組成物を接することを含む。好ましい実施態様は、本発明組成物の一部として光開始剤を含み、脱酸素を所望の速度で開始させるように前記組成物を含むフィルム、層または物品に放射線を当てることを含む。包装フィルムに通常使用されているポリマーを、例えば、１００〜２５０℃で加熱、加工する際に生ずる放射線が脱酸素を誘発しないことが有利である。
The present invention can be used to make various products, compounds, compositions, coatings, and the like. Two preferred forms are sealing compounds and flexible films, both useful for packaging foods or non-foods.
In all of the above applications, by using cyclic olefin copolymers and transition metal catalysts composed of (a) ethylene units and (b) unsubstituted or substituted norbornene compound units, undesired by-products of the deoxygenation reaction Oxygen can be effectively removed from the internal environment of the container while restraining objects.
The method of the present invention comprises contacting the composition with a package cavity containing an oxygen sensitive product. A preferred embodiment includes a photoinitiator as part of the composition of the present invention and includes irradiating the film, layer or article containing the composition to initiate deoxygenation at a desired rate. It is advantageous that the radiation produced when heating and processing the polymers normally used for packaging films, for example at 100 to 250 ° C., does not induce deoxygenation.
初期放射線は好ましくは化学線、例えば２００〜７５０ｎｍ、好ましくは２００〜６００ｎｍ、最も好ましくは２００〜４００ｎｍの波長を有するＵＶまたは可視光である。少なくとも１Ｊ／ｇの放射線、より好ましくは１０〜２０００Ｊ／ｇの放射線を受容するまで脱酸素組成物を含む層、フィルム等を該放射線に暴露させることが好ましい。放射線は少なくとも２キログレイ（ｋＧ）、好ましくは１０〜１００ｋＧの線量の電子ビーム線であってもよい。他の可能性ある放射線ソースにはイオン化放射線、例えば、γ線、Ｘ線及びコロナ放電が含まれる。照射期間は複数の因子に依存するが、これらの因子には存在する光開始剤の量及び種類、照射する層の厚さ、介在する層の厚さ及び不透明度、存在する酸化防止剤の量、放射線ソースの波長及び強度が含まれるが、これらに限定されない。
脱酸素層または物品を使用するとき、その層または物品の製造中またはその後に照射を実施する。作成した層または物品を酸素感受性製品を包装するために使用するならば、包装の直前、その間またはその後に照射する。均一に照射するために、層または物品が平らなシートの形態にある加工段階で照射することが好ましい。
The initial radiation is preferably actinic radiation, for example UV or visible light having a wavelength of 200-750 nm, preferably 200-600 nm, most preferably 200-400 nm. It is preferred to expose the layer, film, etc. comprising the deoxygenated composition to radiation until it receives at least 1 J / g radiation, more preferably 10-2000 J / g radiation. The radiation may be an electron beam beam with a dose of at least 2 kiloGray (kG), preferably 10-100 kG. Other possible radiation sources include ionizing radiation such as gamma rays, x-rays and corona discharges. The duration of irradiation depends on several factors, which include the amount and type of photoinitiator present, the thickness of the layer to be irradiated, the thickness and opacity of the intervening layer, the amount of antioxidant present. Including, but not limited to, the wavelength and intensity of the radiation source.
When using an oxygen scavenging layer or article, irradiation is performed during or after manufacture of the layer or article. If the created layer or article is used to package an oxygen sensitive product, it is irradiated immediately before, during or after packaging. In order to irradiate uniformly, it is preferable to irradiate at a processing stage where the layer or article is in the form of a flat sheet.
特定用途のための所与の脱酸素組成物の脱酸素率及び能力を測定することが有利である。脱酸素率を測定するために、脱酸素剤が密封した容器から特定量の酸素を奪うまでに要した時間を測定する。幾つかの例では、所望の脱酸素組成物を含有するフィルムを酸素含有雰囲気（例えば、通常２０．６容量％のＯ2を含有する空気）の気密性密封容器中に置くことにより十分測定することができる。経時的に、容器内の雰囲気のサンプルを抜き取って酸素の残存率（％）を測定する。通常、測定した脱酸素率は温度及び雰囲気条件により異なる。低い初期酸素含量を有する及び／又は低温条件に維持されている雰囲気では、組成物の脱酸素能力及び脱酸素率がより厳密に試験される。特記しない限り、以下の脱酸素率は室温及び１つの空気雰囲気での値である。活性酸素バリヤーが必要な場合、有用な脱酸素率は空気中２５℃、１ａｔｍで０．０５ｃｍ3−酸素／ｇ−脱酸素組成物中のポリマー／日くらい低くてよい。しかしながら、多くの場合、本発明の組成物は、５．８×１０-6ｃｍ3／ｇ・ｓ（０．５ｃｍ3／ｇ・日）以上、好ましく５．８×１０-5ｃｍ3／ｇ・ｓ（５ｃｍ3／ｇ・日）以上の脱酸素率を有する。更に、本発明の組成物を含むフィルムまたは層は約１．２×１０-4ｃｍ3／ｍ2・ｓ（１０ｃｍ3／ｍ2・日）、場合により約２．３×１０-4ｃｍ3／ｍ2・ｓ（２０ｃｍ3／ｍ2・日）を越える脱酸素率を有する。通常、空気中２５℃、１０１ｋＰａ（１ａｔｍ）で測定したとき、活性酸素バリヤーとして使用するのに好適であると通常見られるフィルムまたは層は１．２×１０-5ｃｍ3／ｍ2・ｓ（１ｃｍ3／ｍ2・日）くらい低い脱酸素率を有する。該脱酸素率により、前記層はパッケージ内から脱酸素するのに好適となり、活性酸素バリヤー用途のために好適となる。 It is advantageous to measure the deoxygenation rate and capacity of a given deoxygenation composition for a specific application. In order to measure the oxygen scavenging rate, the time taken for the oxygen scavenger to take a specific amount of oxygen from the sealed container is measured. In some examples, the film containing the desired deoxygenating composition is well measured by placing it in a hermetically sealed container in an oxygen-containing atmosphere (eg, air typically containing 20.6% by volume O 2 ). be able to. Over time, a sample of the atmosphere in the container is withdrawn, and the residual ratio (%) of oxygen is measured. Usually, the measured deoxygenation rate varies depending on temperature and atmospheric conditions. In an atmosphere having a low initial oxygen content and / or maintained at low temperature conditions, the deoxygenation capacity and deoxygenation rate of the composition is more closely tested. Unless otherwise specified, the following deoxygenation rates are values at room temperature and one air atmosphere. If an active oxygen barrier is required, useful deoxygenation rates may be as low as 0.05 cm 3 -oxygen / g-polymer / day in deoxygenated composition at 25 ° C. in air and 1 atm. However, in many cases, the composition of the present invention is 5.8 × 10 −6 cm 3 / g · s (0.5 cm 3 / g · day) or more, preferably 5.8 × 10 −5 cm 3 / g.・ Deoxygenation rate of s (5 cm 3 / g · day) or more. Further, the film or layer comprising the composition of the present invention is about 1.2 × 10 −4 cm 3 / m 2 · s (10 cm 3 / m 2 · day), optionally about 2.3 × 10 −4 cm 3. Deoxygenation rate exceeding / m 2 · s (20 cm 3 / m 2 · day). Usually, a film or layer normally found to be suitable for use as an active oxygen barrier when measured at 25 ° C. and 101 kPa (1 atm) in air is 1.2 × 10 −5 cm 3 / m 2 · s ( Deoxygenation rate as low as 1 cm 3 / m 2 · day). The deoxygenation rate makes the layer suitable for deoxygenation from within the package and is suitable for active oxygen barrier applications.
本発明の方法を活性酸素バリヤー用途に使用しようとするときには、初期脱酸素活性及び酸素バリヤーにより２５℃で１．１×１０-10 ｃｍ3／ｍ2・ｓ・Ｐａ（１．０ｃｍ3／ｍ2・日・ａｔｍ）未満の全酸素透過率を与えることが好ましい。該値が少なくとも２日間超えないような脱酸素能力が好ましい。
脱酸素が開始したら、脱酸素組成物、該組成物から形成した層または物品は、好ましくはその能力、すなわち脱酸素剤が無効になるまで該脱酸素剤が消費し得る酸素の量まで脱酸素する。実際使用する場合には、所与の用途のために必要な能力はパッケージ中に元々存在する酸素の量、脱酸素性の非存在下でのパッケージへの酸素の進入率及びパッケージの所期の貯蔵寿命に依存する。本発明の組成物を含む脱酸素剤を使用する場合、その能力は１ｃｍ3／ｇくらい低くてもよいが、５０ｃｍ3／ｇ以上にも達し得る。前記脱酸素剤がフィルムの層中に存在するとき、その層は好ましくは少なくとも９．８ｃｍ3／ｍ2／μｍ厚（２５０ｃｍ3／ｍ2／ミル）、より好ましくは少なくとも４７ｃｍ3／ｍ2／μｍ厚（１，２００ｃｍ3／ｍ2／ミル）の酸素能力を有する。
本発明の組成物は、たとえ大量の脱酸素が生じた後でもその物理的特性を実質的に維持するフィルム、層または物品を提供し得る。更に、本発明の組成物は、被包装品に望ましくない味、色及び／又は臭いを与える恐れがある副生成物及び／又は流出物を有意な量生成しない。
When the method of the present invention is to be used in an active oxygen barrier application, it is 1.1 × 10 −10 cm 3 / m 2 · s · Pa (1.0 cm 3 / m) at 25 ° C. due to the initial deoxygenation activity and oxygen barrier. Preferably, the total oxygen transmission rate is less than 2 · day · atm). Deoxygenation capacity is preferred such that the value does not exceed at least 2 days.
Once deoxygenation has begun, the deoxygenated composition, the layer or article formed from the composition, is preferably deoxygenated to its capacity, i.e., the amount of oxygen that the deoxidant can consume until the deoxidant is ineffective. To do. In actual use, the capacity required for a given application is the amount of oxygen originally present in the package, the rate of oxygen entry into the package in the absence of deoxygenation, and the intended package. Depends on shelf life. When using an oxygen scavenger comprising a composition of the present invention, its ability may be low enough 1 cm 3 / g, but can reach to 50 cm 3 / g or more. When said oxygen scavenger is present in the layer of the film, the layers preferably at least 9.8cm 3 / m 2 / μm thickness (250cm 3 / m 2 / mil), more preferably at least 47cm 3 / m 2 / It has an oxygen capacity of μm thickness (1,200 cm 3 / m 2 / mil).
The composition of the present invention can provide a film, layer or article that substantially maintains its physical properties even after a large amount of deoxygenation has occurred. Furthermore, the compositions of the present invention do not produce significant amounts of by-products and / or spills that can impart undesirable taste, color and / or odor to the packaged product.
以下、実施例などに基づき本発明を更に具体的に説明するが、本発明は以下の実施例などに何ら限定されるものではない。ポリマー中のコモノマー含有量はMacromolecules, 31, 4674(1998)に従い、13Ｃ−ＮＭＲスペクトルを用いて行った。ＮＭＲ測定はｄ6−ベンゼン／１，２，４−トリクロロベンゼン（１／１ｖｏｌ比）溶液中で行った。ポリマーのガラス転移温度（Ｔｇ）、融点（Ｔｍ）の測定は示差走査熱量計（ＤＳＣ）を用い、窒素雰囲気下２０℃／分の昇温速度で求めた。
［錯体−１］
（１，３−ジメチルシクロペンタジエニル）トリス（ジメチルジチオカルバミン酸）ジルコニウム（IV）（以下、錯体−１という）の調製
ビス（１，３−ジメチルシクロペンタジエニル）ジルコニウムジクロライド（IV）（２．５ｍｍｏｌ）とジメチルジチオカルバミン酸ナトリウム（７．５ｍｍｏｌ）の原料混合物に塩化メチレン５０ｍｌを加えて、還流温度で２４時間反応した。沈殿をろ過により除いた後、溶媒を濃縮した。塩化メチレン／ｎ−ヘキサンで再結晶して目的錯体を得た。
EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example etc., this invention is not limited to a following example etc. at all. The comonomer content in the polymer was determined according to Macromolecules, 31 , 4674 (1998) using a 13 C-NMR spectrum. NMR measurement was performed in a d 6 -benzene / 1,2,4-trichlorobenzene (1/1 vol ratio) solution. The glass transition temperature (Tg) and melting point (Tm) of the polymer were measured using a differential scanning calorimeter (DSC) at a heating rate of 20 ° C./min in a nitrogen atmosphere.
[Complex-1]
Preparation of (1,3-dimethylcyclopentadienyl ) tris (dimethyldithiocarbamic acid) zirconium (IV) (hereinafter referred to as complex-1) Bis (1,3-dimethylcyclopentadienyl) zirconium dichloride (IV) (2 0.5 mmol) and 50 mL of methylene chloride were added to a raw material mixture of sodium dimethyldithiocarbamate (7.5 mmol) and reacted at reflux temperature for 24 hours. After removing the precipitate by filtration, the solvent was concentrated. Recrystallization from methylene chloride / n-hexane gave the target complex.
［参考例１］
エチレン−ノルボルネン共重合体の調製
内部を真空脱気、窒素置換した２０００ｍｌのオートクレーブ型反応器に、精製したノルボルネンのトルエン溶液６００ｍｌ（ノルボルネンとして４５０ｇ）を導入した。ついでＭＭＡＯ３Ａ（東ソー・ファインケム社製：メチルアルミノキサン）１０ｍｍｏｌを含む精製トルエン溶液１００ｍｌを反応器に導入した後、エチレンガスで０．２ＭＰａに加圧した。反応器の内温を８０℃に保ち、遷移金属錯体として錯体−１を１０μｍｏｌ含む精製トルエン溶液１００ｍｌを反応器に加え重合反応を開始した。反応器の内温およびエチレン圧を保ちつつ、撹拌しながら６０分間重合した。反応器内圧力を大気圧まで落圧し、次いで１Ｎ−ＨＣｌ／ＭｅＯＨ溶液１００ｍｌを反応器内に導入し反応を停止した。
エチレン−ノルボルネン共重合体：収量１０８ｇ、ノルボルネン含量５０ｍｏｌ％、ガラス転移温度Ｔｇ＝１４６℃。
[Reference Example 1]
Preparation of ethylene-norbornene copolymer 600 ml of purified norbornene in toluene (450 g as norbornene) was introduced into a 2000 ml autoclave reactor in which the inside was vacuum degassed and purged with nitrogen. Next, 100 ml of a purified toluene solution containing 10 mmol of MMAO3A (manufactured by Tosoh Finechem Co., Ltd .: methylaluminoxane) was introduced into the reactor, and then pressurized to 0.2 MPa with ethylene gas. The internal temperature of the reactor was kept at 80 ° C., and 100 ml of a purified toluene solution containing 10 μmol of complex-1 as a transition metal complex was added to the reactor to initiate the polymerization reaction. While maintaining the internal temperature of the reactor and ethylene pressure, polymerization was carried out for 60 minutes with stirring. The pressure inside the reactor was reduced to atmospheric pressure, and then 100 ml of 1N HCl / MeOH solution was introduced into the reactor to stop the reaction.
Ethylene-norbornene copolymer: Yield 108 g, norbornene content 50 mol%, glass transition temperature Tg = 146 ° C.
［参考例２］
前述の一般式（１）で表される骨格を有する共重合体である、三井化学（株）が販売している製品名ＡＰＥＬ（レード：ＡＰＬ６０１１Ｔ、ガラス転移温度Ｔｇ＝１０５℃）を入手した。
［参考例３］
前述の一般式（１）で表される骨格を有する共重合体である、ＴＩＣＯＮＡ（株）が販売している製品名ＴＯＰＡＳ（グレード：８００７、ノルボルネン含量３６ｍｏｌ％、ガラス転移温度Ｔｇ＝８２℃）を入手した。
［錯体−２］
ラセミ体エチレンビス（インデニル）二塩化ジルコニウム（ＩＶ）
アヅマックス（株）から購入し、そのまま使用した（以下、錯体−２という）。
[Reference Example 2]
The product name APEL (Rade: APL 6011T , glass transition temperature Tg = 105 ° C.) sold by Mitsui Chemicals, Inc., which is a copolymer having a skeleton represented by the general formula (1), was obtained. .
[Reference Example 3]
Product name TOPAS (grade: 8007 , norbornene content: 36 mol%, glass transition temperature: Tg = 82 ° C.) sold by TICONA, which is a copolymer having a skeleton represented by the above general formula (1) Was obtained.
[Complex-2]
Racemic ethylenebis (indenyl) zirconium dichloride (IV)
It was purchased from Amax Co., Ltd. and used as it was (hereinafter referred to as Complex-2).
［参考例４］
エチレン−シクロペンテン共重合体の調製
内部を真空脱気、窒素置換した２０００ｍｌのオートクレーブ型反応器に、精製したシクロペンテンの４．５Ｍトルエン溶液６００ｍｌ（シクロペンテンとして１８４ｇ）を導入した。次いでＭＭＡＯ３Ａ（東ソー・ファインケム社製：メチルアルミノキサン）１０ｍｍｏｌを含む精製トルエン溶液１００ｍｌを反応器に導入した後、エチレンガスで０．１ＭＰａに加圧した。反応器の内温を５０℃に保ち、遷移金属錯体として錯体−２を５μｍｏｌ含む精製トルエン溶液１００ｍｌを反応器に加え重合反応を開始した。反応器の内温およびエチレン圧を保ちつつ、撹拌しながら１２０分間重合した。反応器内圧力を大気圧まで落圧し、次いで１Ｎ−ＨＣｌ／ＭｅＯＨ溶液１００ｍｌを反応器内に導入し反応を停止した。
エチレン−シクロペンテン共重合体：収量１１７ｇ、シクロペンテン含量１０ｍｏｌ％、分子量Ｍｎ＝３．５×１０3、ガラス転移温度Ｔｇ＝−１４℃、融点Ｔｍ＝６８℃。
[Reference Example 4]
Preparation of ethylene-cyclopentene copolymer 600 ml of a 4.5M toluene solution of purified cyclopentene (184 g as cyclopentene) was introduced into a 2000 ml autoclave reactor in which the inside was vacuum degassed and purged with nitrogen. Next, 100 ml of a purified toluene solution containing 10 mmol of MMAO3A (manufactured by Tosoh Finechem Corporation: methylaluminoxane) was introduced into the reactor, and then pressurized to 0.1 MPa with ethylene gas. The internal temperature of the reactor was kept at 50 ° C., and 100 ml of a purified toluene solution containing 5 μmol of complex-2 as a transition metal complex was added to the reactor to initiate the polymerization reaction. While maintaining the reactor internal temperature and ethylene pressure, polymerization was carried out for 120 minutes with stirring. The pressure inside the reactor was reduced to atmospheric pressure, and then 100 ml of 1N HCl / MeOH solution was introduced into the reactor to stop the reaction.
Ethylene-cyclopentene copolymer: Yield 117 g, cyclopentene content 10 mol%, molecular weight Mn = 3.5 × 10 3 , glass transition temperature Tg = −14 ° C., melting point Tm = 68 ° C.
［実施例１〜３、比較例１］
参考例１〜４のポリマーを、１０００ｐｐｍのオレイン酸コバルト（II）塩及び１０００ｐｐｍの４、４'−ジメチルベンゾフェノン（ＤＭＢＰ）とを窒素パージ下に溶融混合した。圧縮成型によって１２０ｍｍ×１２０ｍｍ×０．５ｍｍｔの平板を作成した。１００ｍｍ角に裁断し総表面積が約２００００ｍｍ2（１００ｍｍ×１００ｍｍ＝１００００ｍｍ2／面）の試験片とした。酸素補足性ポリマーを活性化するためにUVA（１１７０ｍＪ／ｃｍ2）及びＵＶＣ（８００ｍＪ／ｃｍ2）を約９０秒間照射した。試験片はアルミニウム箔多層シート製の四方パウチに収め、パウチ内の酸素濃度の経時変化を冷却ヘッドスペース捕集試験（refrigerated headspace scavenging test）及び平行室温試験（parallel room temperature test）を用いて調べた。冷却ヘッドスペース試験（４℃）では、試験片を窒素約９９％及び酸素１％の混合物の雰囲気３００ｃｍ3を収容しているパウチ内に入れた。室温試験（２０℃）では、試験片を空気（窒素中２０．６％酸素）３００ｃｍ3を収容しているパウチ内に入れた。パウチ内の酸素含量％をＭＯＣＯＮ（商標）：ＬＣ７００Ｆ酸素アナライザーを用いて分析した。結果を表１、表２に示す。
[Examples 1 to 3, Comparative Example 1]
The polymers of Reference Examples 1 to 4 were melt mixed with 1000 ppm of cobalt (II) oleate and 1000 ppm of 4,4′-dimethylbenzophenone (DMBP) under a nitrogen purge. A flat plate of 120 mm × 120 mm × 0.5 mmt was prepared by compression molding. A test piece having a total surface area of about 20000 mm 2 (100 mm × 100 mm = 10000 mm 2 / surface) was cut into a 100 mm square. The UVA (1170mJ / cm 2) and UVC (800mJ / cm 2) was irradiated for about 90 seconds in order to activate the oxygen supplemental polymer. The test piece was placed in a four-sided pouch made of an aluminum foil multilayer sheet, and the change over time in the oxygen concentration in the pouch was examined using a refrigerated headspace scavenging test and a parallel room temperature test. . In the cooling headspace test (4 ° C.), the specimen was placed in a pouch containing an atmosphere of 300 cm 3 of a mixture of about 99% nitrogen and 1% oxygen. In the room temperature test (20 ° C.), the test piece was placed in a pouch containing 300 cm 3 of air (20.6% oxygen in nitrogen). The oxygen content% in the pouch was analyzed using a MOCON ™: LC700F oxygen analyzer. The results are shown in Tables 1 and 2.
本発明の組成物によって、優れた脱酸素能力を有した酸素感受性製品を包装するために使用されうるフィルムまたは物品材料を提供することが可能となった。 The composition of the present invention has made it possible to provide a film or article material that can be used to package an oxygen sensitive product with excellent deoxygenation capabilities.
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